Treatment of textile fabrics



55 question any strong auxochromic effect.

Patented Mar. 12, 1940 PATENT OFFICE TREATMENT OF TEXTILE FABRICS Henry Charles Olpin and George Holland Ellis, Spondon, near Derby, England, assignors to Celanese Corporation of America, a corporation of Delaware No Drawing.

Application March 29, 1938, Serial No. 19$,686. In Great Britain April 9, 1937 13 Claims.

This invention relates to the treatment of textile fabrics, and particularly to the production of coloured effects on textile fabrics containing yarns of cellulose acetate or other organic derivatives of cellulose.

In U. S. applications S. Nos. 39,288, 39,239 and 39,290 filed 5th September, 1935, processes are described wherein filaments, yarns, fabrics and similar materials having a basis of organic derivatives of cellulose are subjected to esterification. Thus, for example, filaments, yarns or fabrics having a basis of cellulose acetate may be subjected to an acetylation treatment. As indicated in the said specifications, the materials so producedhave, in general, a somewhat reduced affinity for the dyestuffs commonly employed in dyeing cellulose acetate materials so that it is possible to produce cross-dyed effects by associating together in a fabric ordinary yarns of organic derivatives of cellulose and yarns of organic derivatives of cellulose which have been esterified, and dyeing the fabric with the ordinary dyestuffs used for cellulose acetate materials. The result is to produce a fabric in which the two types of yarn are dyed to different depths, the ordinary yarn of organic derivative of cellulose being dyed the deeper shade.

It has now been discovered that certain classes of dyestuffs which have affinity for ordinary yarns ll of organic derivatives of cellulose have little or no afiinity for yarns of organic derivatives of cellulose which havebeen esterified and that, in consequence, by treating with such dyestufis fabrics which contain both ordnary yarns of organic 35 derivatives of cellulose and yarns of organic derivatives of cellulose which have been esterified products may be obtained in which the ordinary yarns are coloured and the esterified yarns are uncoloured by the treatment.

40 The invention is of greatest importance'in connection with the production of fabrics exhibiting coloured effects Where the-fabrics containyarns of cellulose acetate of acetyl content 52-55% (the ordinary acetate silk of commerce), and also I I yarns of this character which have been subjected to acetylation by one of the processes of the abovementioned specifications, and the invention will therefore Joe-described with particular reference to the treatment of such fabrics.

0 The dyestuffs found to be of value for the purpose of this invention are dyestuffs which have aflinity for yarns of-cellulose acetate of 52-55% acetyl content and which contain hydrophile groups which do not possess in the dyestuffs in Of particular value are dyestuffs of this type which are sufliciently soluble in water to permit of their being applied from aqueous solution. As examples of hydrophile groups there may be mentioned sulphonic acid groups, sulphuric acid ester groups, aliphatic hydroxy groups and carboxyl groups. In general the dyestuffs should not contain more than one sulphonic acid, sulphuric acid ester or carboxyl group, though in the case of dyestuffs containing aliphatic hydroxy groups two or more of such groups are permissible. As examples of suitable dyestufis containing a sulphonic acid group there may be mentioned l-amino-l-phenylaminoanthraquinone-Z-sulphonic acid, 4' (2 :4-dinitrophenylamino) -4-methyl-diphenylamine 6 sulphonic acid, 2:6 dinitro benzene 4 sulphonic acid-azo-pmaphthylamine, and 4-nitro-2-w-sulpho methyl benzene-azo ethylbenzylaniline. Suitable dyestufis containing aliphatic hydroxy groups are, for example, anthraquinone dyestuffs containing nuclear hydroxyalkyl, hydroxyalkyl oxy, or hydroxyalkylamino groups and azo dyestuffs obtained by diazotising aniline or its homologues, or their nitro or halogen substitution products, and coupling the diazotised compounds so obtained with amino coupling components containing hydroxyalkyl groups, for example amino coupling components in which the amino group 1 is substituted by an hydroxyalkyl group and an alkyl group. As examples of such dyestuffs there may be mentioned 1:4 diethanolamino anthraquinone and 1:4-diethanolamino-5-hydroxy-anthraquinone. Suitable dyestuffs containing sulphuric acid ester groups are the sulphuric acid esters of dyestuffs containing single aliphatic by,

droxy'groups. As examples there may be mentioned the sulphuric acid esters of l-methylamino- 4-ethanolamino-anthraquinone, of 4-nitro-ben-' zene-azo-ethyl hydroxyethyl aniline and of 4- nitro-2-chlorbenzene-azo-ethyl-hydroxyethyl-aniline.

The dyeing is preferably effected by treatment of the fabric with an aqueous dye liquor at a temperature below the boiling point of the liquor, e. g. at a temperature not above about 80 C.'and it is preferable that the conditions should be such that no substantial swelling of the esterified yarns takes place.

The fabric treated according to this invention may contain the ordinary yarns of organic derivatives of cellulose, and yarns of organic derivatives of cellulose which have been esterified,

" associated together in any wayp-"Ihus, for example, the warp yarns, or part of the warp yarns,

yarns, may be yarns of organic derivatives of cellulose which have been esterified, or vice versa. The two types of yarn may be associated together so that one type of yarn forms any desired pattern on a background of the other type of yarn. Again, the fabric may be formed from ordinary yarns of organic derivatives of cellulose and subjected to a process of local esterification in any desired pattern. Or, again, the fabric may contain mixed yarns which contain some ordinary filaments of organic derivatives of cellulose and some filaments of organic derivatives of cellulose which have been subjected to esterification, e. g. doubled yarns of which one constituent yarn is an ordinary organic derivative of cellulose yarn and the other is an organic derivative of cellulose yarn which has been subjected to esterification.

The esterified yarn present in the fabric may have been esterified by any suitable process. Of particular value, however, are yarns produced by the processes described in the specifications referred to above. The esterified yarn should be, or should approxime te to, a tri-substitution product of cellulose. For example, in the case of acetylated cellulose acetate yarn the product should have an acetyl value of 59% or 60% or more. calculated as acetic acid.

The process of the invention may be modified, if desired, so that the esterified yarns of organic derivatives of cellulose in the final product, instead of being white, are also coloured. One way of achieving this result is to dye the esterified yarns of organic derivatives of cellulose with a suitable dyestulf before converting them into the fabric. Another way is to subject the esterified yarns to a process of superficial saponification before converting them into a fabric. In this way the esterified yarns, while still remaining unafiected by the dyestuffs used for colouring the ordinary yarns of organic derivatives of cellulose, acquire an affinity for direct dyestuffs, e. g. the dyestuffs commonly employed in the manufacture of cotton. Thus, for example, a fabric formed by associating together ordinary yarns of organic derivatives of cellulose and yarns of organic derivatives of cellulose which have been esterified and superficially saponified may be treated with a dyestuif of the type indicated above which will colour the ordinary yarns of organic derivatives of cellulose without colouring the esterified yarns, and also with a cotton dyestuff in order to colour the esterified and superficially saponified yarns. These dyestuffs may be applied in either order or simultaneously. The following example illustrates the invention but is not to be regarded as limiting it in any way:

Example A fabric containing yarns of cellulose acetate of 52-54% acetyl content, and also similar yarns which have been acetylated by one of the proc esses of the specifications referred to above to an acetyl value of 60-62.5%, is immersed in an aqueous bath which is 30 times the weight of thefabric treated and which contains 40% of sodium sulphate on the weight of 'the fabric treated and 1% of 4'-(2:4-dinitrophenylamino)- 4-methyl-diphenylamine-6'-sulphonic acid on the weight of the fabric treated. The dye bath is ,maintained at C. After dyeing is completed the fabric is scoured and dried. The yarns of cellulose acetate of 52-54% acetyl content are dyed a good yellow shade while the yarns which have been acetylated are uncoloured.

Similar results are obtained by substituting for the dyestufl used in this example one of the following dyestuffs:

The sulphuric acid ester of 4-nitro-benzene-azoethyl-hydroxyethyl-aniline; the sulphuric acid ester of 4-nitro-2-chlor-benzene-azo-ethyl-hydroxyethyl-aniline; 1 amino-*l-phenylaminoanthroquinone-2-sulphonic-acid.

. effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuff for the former yarns, by

subjecting said fabric to the action of a dye liquid containing a dyestufi which has affinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect .in the dyestuif.

2. Process for the production of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of cellulose acetate of acetyl value 52 to 55% calculated as acetic acid and similar yarns which have been esterified to an acidyl value corresponding to 2.7 to 3 acidyl radicles per Cs H1005 unit, so as to effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuif for the former yarns, by subjecting said fabric to the action of a dye liquid containing a water-soluble dyestuff which has affinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect in the dyestuif.

3. Process for the production of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of cellulose acetate of acetyl value 52 to 55% calculated as acetic acid and similar yarns which have been esterified to an acidyl value corresponding to 2.7 to 3 acidyl .radicles per CsHmOs unit, so as to effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuif for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestuif which has amnity for the former yarns and which contains a single group containing the radicle SOz.OH.

4. Process for the production of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of cellulose acetate of acetyl value 52 to 55% calculated as acetic acid and similar yarns which have been esterified to an acidyl value corresponding to 2.7 to 3 acidyl radicles per C6H1005 unit, so as to effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestufi for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestuif which has aflinity for the former yarns and which contains a single sulphuric acid ester group.

5. Process for the production of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of cellulose acetate of acetyl value 52 to 55% calculated as acetic acid and similar yarns which have been success esterified to an acidyl value corresponding to 2.7 to 3 acidyl radicles per (361-11005 unit, so as to effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuff for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestuif which has amnity for the former yarns and which contains at least two aliphatic hydroxy groups.

6. Process for the production of fabrics exhibiting colored eifects, which comprises treating, at a temperature which is at most about 80 C., a fabric containing both yarns of cellulose acetate of acetyl value 52 to 55% calculated as acetic acid and similar yarns which have been esterifled to an acidyl value corresponding to 2.7 to 3 acidyl radicles per CaHmOs unit, so as to effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuff for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestuif which has amnity for the former yarns and which contains a hydrophile group which has no strong auxochromi'c effect in the dyestufi.

'7. Process for the production of fabrics exhibiting colored effects, which comprises treating, at a temperature which is at most about 80 C., a fabric containing both yarns of cellulose acetate of acetyl value 52-55%, calculated as acetic acid, and similar yarns which have been esteriiied to an acidyl value corresponding to 2.7 to 3 acidyl-radicles per CcHmOs unit, so as to effect coloration of the former yarns without efiecting any substantial coloration of the latter yarns with the dyestufl" for the former yarns, by subjecting said fabric to the action of a dye liquid containing a water-soluble dyestuif which has aflinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect in the dyestufl.

8. Process for the production of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of cellulose acetate of acetyl value 52-55% calculated as acetic acid, and similar yarns which have been esterified to an acidyl value corresponding to 2.7-3 acidyl radicles per Cal-11005 radicle and colored before being incorporated in the fabric, so as to eifect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuif for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestuif which has amnity for the former yarns and which contains a hydrophile group which has no strong auxochromic eifec't in the dyestuif.

9. Process for the production of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of an organic den'vative of cellulose which is soluble in organic solvents and similar yarns which have been esteriiied to an acidyl value corresponding to 2.7 to 3 acidyl radicles per CcHmOs unit and subwith the dyestufl for the former yarns, by sub-- jecting said fabric to the action of a dye liquid containing a dyestuff which has aihnity for the former yarns and which contains a hydrophile group which has no strong auxochromic eflect in the dyestufi'.

10. Process for the production of fabrics exhibiting colored eflects, which comprises treating a fabric containing both yarns of cellulose acetate of acetyl value 52-55%, calculated as acetic acid, and similar yarns which have been esterifled to an acidyl value corresponding to 2.7 to 3 acidyl radicles per CsHmOs unit and subsequently superficially saponified, so as to eifect coloration of the former yarns without eifecting any substantial coloration of the latter yarns with the dyestuif for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestufi which has aiiinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect in the dyestuff.

11. Process for the production of fabrics exhibiting colored effects, which comprises treating, at a temperature of at most about 80 C., a

fabric to the action of a dye liquid containing a water-soluble dycstuff which has affinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect in the dyestufl'.

'12. Process for the production of fabrics exhibiting colored effects which comprises treating a fabric containing both yarns of an organic derivative of cellulose which is soluble in organic solvents and similar yarns which have been esterifled until they contain from 2.7 to 3 substituent radicles per CsHmOs unit so as to effect coloration of the former yarns without effecting any substantial coloration of the latter yarns with the dyestuif for the former yarns, by subjecting said fabric to the action of a dyeliquid containing a dyestufl which has aflinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect in the dyestuif. V

13. Process for theproduction of fabrics exhibiting colored effects, which comprises treating a fabric containing both yarns of acetone-soluble cellulose acetate and similar yarns which have been esteriiied to an acidyl value corresponding 1 to 2!! to 3 acidyl radicles per CsHroOs unit,.so

as to effect coloration of the former yarns without efiecting any substantial coloration of the latter yarns with the dyestuif for the former yarns, by subjecting said fabric to the action of a dye liquid containing a dyestufl which has aflinity for the former yarns and which contains a hydrophile group which has no strong auxochromic effect in the dyestuii.-

' HENRY CHARLES OLPIN.

GEORGE HOLLAND ELLIS. 

